[0001] The present invention relates to displays incorporating multi-color electro-optic
media.
[0002] The term "electro-optic", as applied to a material or a display, is used herein in
its conventional meaning in the imaging art to refer to a material having first and
second display states differing in at least one optical property, the material being
changed from its first to its second display state by application of an electric field
to the material. The optical property is typically color perceptible to the human
eye.
[0003] The term "gray state" is used herein in its conventional meaning in the imaging art
to refer to a state intermediate two extreme optical states of a pixel, and does not
necessarily imply a black-white transition between these two extreme states. For example,
several of the E Ink patents and published applications referred to below describe
electrophoretic displays in which the extreme states are white and deep blue, so that
an intermediate "gray state" would actually be pale blue. The terms "black" and "white"
may be used hereinafter to refer to the two extreme optical states of a display, and
should be understood as normally including extreme optical states which are not strictly
black and white, for example the aforementioned white and dark blue states. The term
"monochrome" may be used hereinafter to denote a drive scheme which only drives pixels
to their two extreme optical states with no intervening gray states.
[0004] The terms "bistable" and "bistability" are used herein in their conventional meaning
in the art to refer to displays comprising display elements having first and second
display states differing in at least one optical property, and such that after any
given element has been driven, by means of an addressing pulse of finite duration,
to assume either its first or second display state, after the addressing pulse has
terminated, that state will persist for at least several times, for example at least
four times, the minimum duration of the addressing pulse required to change the state
of the display element. It is shown in
U.S. Patent No. 7,170,670 that some particle-based electrophoretic displays capable of gray scale are stable
not only in their extreme black and white states but also in their intermediate gray
states, and the same is true of some other types of electro-optic displays. This type
of display is properly called "multi-stable" rather than bistable, although for convenience
the term "bistable" may be used herein to cover both bistable and multi-stable displays.
[0005] Several types of electro-optic displays are known, for example:
- (a) a rotating bichromal member type as described, for example, in U.S. Patents Nos. 5,808,783; 5,777,782; 5,760,761; 6,054,071 6,055,091; 6,097,531; 6,128,124; 6,137,467; and 6,147,791;
- (b) an electrochromic medium, for example an electrochromic medium in the form of
a nanochromic film comprising an electrode formed at least in part from a semi-conducting
metal oxide and a plurality of dye molecules capable of reversible color change attached
to the electrode; see, for example O'Regan, B., et al., Nature 1991, 353, 737; and Wood, D., Information Display, 18(3), 24 (March 2002). See also Bach, U., et al., Adv. Mater., 2002, 14(11), 845; and
- (c) an electro-wetting display developed by Philips and described in Hayes, R.A., et al., "Video-Speed Electronic Paper Based on Electrowetting", Nature,
425, 383-385 (2003). It is shown in U.S. Patent No. 7,420,549 that such electro-wetting displays can be made bistable.
[0006] Particle-based electrophoretic displays, in which a plurality of charged particles
move through a fluid under the influence of an electric field, have been the subject
of intense research and development for a number of years. Electrophoretic displays
can have attributes of good brightness and contrast, wide viewing angles, state bistability,
and low power consumption when compared with liquid crystal displays. Nevertheless,
problems with the long-term image quality of these displays have prevented their widespread
usage. For example, particles that make up electrophoretic displays tend to settle,
resulting in inadequate service-life for these displays.
[0007] As noted above, electrophoretic media require the presence of a fluid. In most prior
art electrophoretic media, this fluid is a liquid, but electrophoretic media can be
produced using gaseous fluids; see, for example,
Kitamura, T., et al., "Electrical toner movement for electronic paper-like display",
IDW Japan, 2001, Paper HCS1-1, and
Yamaguchi, Y., et al., "Toner display using insulative particles charged triboelectrically",
IDW Japan, 2001, Paper AMD4-4). See also
U.S. Patents Nos. 7,321,459 and
7,236,291. Such gas-based electrophoretic media appear to be susceptible to the same types
of problems due to particle settling as liquid-based electrophoretic media, when the
media are used in an orientation which permits such settling, for example in a sign
where the medium is disposed in a vertical plane. Indeed, particle settling appears
to be a more serious problem in gas-based electrophoretic media than in liquid-based
ones, since the lower viscosity of gaseous suspending fluids as compared with liquid
ones allows more rapid settling of the electrophoretic particles.
[0008] Numerous patents and applications assigned to or in the names of the Massachusetts
Institute of Technology (MIT) and E Ink Corporation describe various technologies
used in encapsulated electrophoretic and other electro-optic media. Such encapsulated
media comprise numerous small capsules, each of which itself comprises an internal
phase containing electrophoretically-mobile particles in a fluid medium, and a capsule
wall surrounding the internal phase. Typically, the capsules are themselves held within
a polymeric binder to form a coherent layer positioned between two electrodes. The
technologies described in the these patents and applications include:
- (a) Electrophoretic particles, fluids and fluid additives; see for example U.S. Patents Nos. 7,002,728; and 7,679,814;
- (b) Capsules, binders and encapsulation processes; see for example U.S. Patents Nos. 6,922,276 and; 7,411,719;
- (c) Films and sub-assemblies containing electro-optic materials; see for example U.S. Patents Nos. 6,982,178; and 7,839,564;
- (d) Backplanes, adhesive layers and other auxiliary layers and methods used in displays;
see for example U.S. Patents Nos. 7,116,318; and 7,535,624;
- (e) Color formation and color adjustment; see for example U.S. Patents Nos. 6,017,584; 6,664,944; 6,864,875; 7,075,502; 7,167,155; 7,667,684; and 7,791,789; and U.S. Patent Applications Publication Nos. 2004/0263947; 2007/0109219; 2007/0223079; 2008/0023332; 2008/0043318; 2008/0048970; 2008/0211764; 2009/0004442; 2009/0225398; 2009/0237776; 2010/0103502; 2010/0156780; and 2010/0225995;
- (f) Methods for driving displays; see for example U.S. Patents Nos. 7,012,600; and 7,453,445;
- (g) Applications of displays; see for example U.S. Patent No. 7,312,784; and U.S. Patent Application Publication No. 2006/0279527.
[0009] Many of the aforementioned patents and applications recognize that the walls surrounding
the discrete microcapsules in an encapsulated electrophoretic medium could be replaced
by a continuous phase, thus producing a so-called polymer-dispersed electrophoretic
display, in which the electrophoretic medium comprises a plurality of discrete droplets
of an electrophoretic fluid and a continuous phase of a polymeric material, and that
the discrete droplets of electrophoretic fluid within such a polymer-dispersed electrophoretic
display may be regarded as capsules or microcapsules even though no discrete capsule
membrane is associated with each individual droplet; see for example,
U.S. Patent No. 6,866,760. Accordingly, for purposes of the present application, such polymer-dispersed electrophoretic
media are regarded as sub-species of encapsulated electrophoretic media.
[0010] A related type of electrophoretic display is a so-called "microcell electrophoretic
display". In a microcell electrophoretic display, the charged particles and the fluid
are not encapsulated within microcapsules but instead are retained within a plurality
of cavities formed within a carrier medium, typically a polymeric film. See, for example,
U.S. Patents Nos. 6,672,921 and
6,788,449, both assigned to Sipix Imaging, Inc. Hereinafter, the term "microcavity electrophoretic
display" may be used to cover both encapsulated (including polymer-dispersed) and
microcell electrophoretic displays.
[0011] Although electrophoretic media are often opaque (since, for example, in many electrophoretic
media, the particles substantially block transmission of visible light through the
display) and operate in a reflective mode, many electrophoretic displays can be made
to operate in a so-called "shutter mode" in which one display state is substantially
opaque and one is light-transmissive. See, for example,
U.S. Patents Nos. 5,872,552;
6,130,774;
6,144,361;
6,172,798;
6,271,823;
6,225,971; and
6,184,856. Dielectrophoretic displays, which are similar to electrophoretic displays but rely
upon variations in electric field strength, can operate in a similar mode; see
U.S. Patent No. 4,418,346. Electrophoretic media operating in shutter mode may be useful in multi-layer structures
for full color displays; in such structures, at least one layer adjacent the viewing
surface of the display operates in shutter mode to expose or conceal a second layer
more distant from the viewing surface.
[0012] There is today an increasing demand for color in all displays. Users familiar with
color televisions, color computer displays and color displays on cellular telephones
and other portable electronic devices may regard monochrome display as lacking something
in visual appeal even in applications such as electronic book readers, where the display
aims to reproduce the look of a printed book, most of which are still printed in monochrome.
[0013] In conventional printing, full color images of high quality are formed by providing
sub-images in each of three subtractive primary colors, typically cyan, magenta and
yellow ("CMY") (black may be included as a four primary in a "CMYK" system) that are
overlaid (i.e., more than one color can be present at any point on the page) in such
a way that light is filtered through each sub-image before being reflected back from
the underlying white paper to the viewer. (Thus, a so-called "four color", CMYK system
is in reality a five-color system; the white color of the underlying paper is part
of the color formation system, as is readily appreciated from the fact that this white
color appears where no ink whatever is present.) In this arrangement of three or four
overlaid sub-images, no area of the printed paper absorbs light unnecessarily, and
thus an image of maximum brightness is obtained.
[0014] Prior art electrophoretic and similar electro-optic displays have typically relied
upon the use of reflective (light-scattering) pigments. Since no substantial amount
of light passes through a layer of such pigment, it is not possible to overlay sub-images
of differing colors, and in a color display it is necessary to resort to "color area
sharing" to render a palette of colors. For example, multiple different sub-regions
of the display may be provided with electrophoretic media capable of displaying different
colors, for example red, green and blue. (Note that since there is no overlaying of
sub-images of different colors, this type of display typically uses additive primaries
rather than subtractive primaries.) Alternatively, a monochrome medium can be used
and a color filter array provided so that specific pixels can reflect specific primary
colors. Either approach suffers, however, from the problem that only a fraction of
the area of the display is available for reflection of each primary color, which adversely
affects the brightness of the image available. Hence, to improve the brightness of
a color reflective display, it is desirable to provide a display which can display
any desired color at any pixel of the display, and thereby to maximize the amount
of light reflected to a viewer.
[0015] Multilayer, stacked electro-optic displays using are known in the prior art. In such
displays, ambient light passes through sub-images in each of the three subtractive
primary colors, in a manner analogous to conventional color printing. United States
Patent No.
6,727,873 describes a stacked electrophoretic display in which three layers of switchable cells
are placed over a reflective background. Similar displays are known in which pigments
are moved laterally; see for example International Application Publication No.
WO 2008/065605) or, pigments in microcavities are moved using a combination of vertical and lateral
motion. For a review of such displays, see
J. Heikenfeld, P., et al., Journal of the SID, 19(2), 2011, pp. 129-156. In these prior art displays, each pixel of each layer must be capable of being driven
independently so as to concentrate or disperse the pigment particles on a pixel-by-pixel
basis. This requires three separate pair of electrodes, each of which typically comprises
an active matrix backplane having a matrix of thin-film transistors, and an opposed
continuous counter-electrode. Two of the active matrix backplanes must be as transparent
as possible, as must be each counter-electrode. This approach suffers from the severe
disadvantages of the high cost of manufacturing such a complex arrangement of electrodes,
and from the fact that in the present state of the art it is difficult to provide
an adequately transparent backplane, especially as the white state of the display
requires that light pass through several layers of such transparent electrodes; in
practice, the light losses in the electrodes have a severe adverse effect on the brightness
of the image produced by the display.
[0016] Those skilled in the imaging art know that it is necessary to provide independent
addressing of each primary color in order to render a full-color image. This is illustrated
graphically in Figure 1 of the accompanying drawings, which shows a "color cube" in
which the vertices correspond to white, the three subtractive primary colors (yellow,
magenta, and cyan), the three additive primary colors (red, green and blue) and black.
As shown by the arrows, any point inside or on the surface of the color cube can be
defined by three (orthogonal) co-ordinates, namely, the distances along the white-yellow
axis, the white-magenta axis, and the white-cyan axis. These distances correspond
to different optical densities in the subtractive primary colors, ranging from zero
(i.e., white) to about 2 (corresponding 99% absorption of light of the corresponding
additive primary spectral range). The number of discretely addressed independent states
required to render the full color gamut of a display is the number of yellow states
plus the number of magenta states plus the number of cyan states. The number of colors
that can be rendered, however, is the product of these three numbers. Thus, for example,
a display may be chosen to render 2 yellow states (since the human visual system is
relatively insensitive to spatial variation in blue light, the absence of which corresponds
to the yellow subtractive primary color) and 2
4 = 16 states of each of magenta and cyan. The waveform driving the display would be
required to render 34 different states in total, but would be able to address 2
9 = 512 different colors.
JP H06 265854 A describes a reflection type liquid crystal display comprising three stacked liquid
crystal layers disposed between a single pair of electrodes with no electrodes between
the adjacent pairs of liquid crystal layers. The three liquid crystal layers are capable
of displaying different colors.
WO 2007/007218 A2 describes a light modulator comprising (in the embodiment of Figure 9) four stacked
electrophoretic layers disposed between a single set of electrodes, with no electrodes
between adjacent pairs of electrophoretic layers. The four electrophoretic layers
contain particles of differing colors, for example yellow, cyan, magenta and black.
This document discloses the features of the preamble of claim 1.
US 2007/0195399 A1 describes an electrophoretic display comprising (in the embodiment of Figure 6) two
stacked electrophoretic layers with no electrode between the two layers but with an
electrical field isolation layer disposed between the two layers. Each layer is driven
by a pair of electrodes on the outer surface of the layer.
US 2008/0117495 describes a dielectrophoretic display comprises a substrate having walls defining
at least one cavity, the cavity having a viewing surface and a side wall inclined
to the viewing surface; a suspending fluid contained within the cavity; two different
types of particles having differing colors suspended within the suspending fluid;
and means for applying to the substrate an electric field effect effective to cause
dielectrophoretic movement of the particles to the side wall of the cavity. Each type
of particles has a shuttered state, in which it occupies substantially the entire
area of the cavity, and an unshuttered state, in which the particles occupy only a
minor proportion of the area of the cavity.
[0017] This invention can provide a color display in which a single pair of electrodes are
used to address independently more than one layer of electrophoretic or similar electro-optic
material. Such a color display can provide independent, or at least partially independent
addressing of more than one primary color using a single pair or single set of electrodes
(for example, the single set of electrodes can be an active matrix backplane and a
single continuous counter-electrode. At least one of the layers of electrophoretic
or similar material may operate in shutter mode (as defined above).
[0018] Shutter mode electrophoretic displays can be used as light modulators, including
variable transmission ("VT") windows. Light modulators represent a potentially important
market for electro-optic media. VT media capable of being used as VT windows have
been demonstrated and are described in the patent literature; see, for example,
U. S. Patent No. 7,327,511; and
U.S. Patent Applications Publication Nos. 2006/0038772;
2007/0146310; and
2008/0130092. However, there are certain remaining problems in such VT media. Firstly, it is difficult
to achieve in the same medium acceptable levels of image stability (i.e., stable transmission)
and haze. To date, no black pigment has been identified which has a refractive index
close enough to that of the fluids typically used in electrophoretic media (or close
enough to that of the polymeric phase which typically surrounds the fluid, as discussed
above) to reduce haze to an acceptable level.
[0019] Another problem with prior art VT electrophoretic media (and similar electro-optic
media such as electrochromic media) is their inability to vary hue; in other words,
the colors capable of being displayed by such media fall on a line between their endpoint
colors (a transparent state being regarded as a "color" for purposes of the present
application), and the media do not have a color gamut volume. For example, the colors
obtainable from the VT media described in the aforementioned
U. S. Patent No. 7,327,511; and
U.S. Patent Applications Publication Nos. 2006/0038772;
2007/0146310; and
2008/0130092 vary from black to clear, while electrochromic media typically vary from blue-purple
to clear. (Provision of color in VT media may be useful either in enabling the light
within a room equipped with VT windows to be varied, or in enabling the use of VT
as one layer in a multi-layer display, as discussed in detail below.) Neither type
of media can produce additional colors without the addition of a color filter array,
and the use of a multi-pixel drive method, typically using a passive or active matrix
backplane. Such a backplane inevitably reduces optical transmission through the VT
medium and is far more expensive than the simple electrode used in a single pixel
VT display
[0020] Accordingly, there is still a need for a VT medium which can provide the high image
stability desirable in commercial VT displays in combination with low haze. There
is also still a need for VT media which can provide a substantial color gamut. In
one aspect, the present invention seeks to provide solutions to both these problems.
[0021] This invention provides an electro-optic display comprising first and second layers
of cavities disposed adjacent one another with no electrode between the first and
second layers, the sections of each of first and second layers of cavities lying adjacent
the other layer being of substantially pyramidal form tapering towards the other layer,
at least one of the first and second layers comprising colored particles dispersed
in a fluid and capable of moving through the fluid on application of an electric field
to the display. In such a display, the first and second layers may be formed of deformable
capsules. One of the first and second layers may be free from colored particles.
[0022] The display of the invention may further comprise a first electrode disposed on one
side of the first and second layers, and a second electrode disposed on the opposed
side of the first and second layers from the first electrode. (The term "electrode"
is used herein in its conventional meaning in the electro-optic display art to mean
a conductive material the electrical potential of which can be controlled by being
connected to a source of known potential, including ground. Thus, for purposes of
this application, a conductive material not arranged to be connected to any source
of known potential is not an electrode.)
[0023] Such a display may further comprises a third layer of electro-optic material, the
third layer being capable of displaying at least one optical state which cannot be
displayed by the first and second layers, the second electrode being disposed on the
opposed side of the first, second and third layers from the first electrode, there
being no electrode between the second and third layers. The three layers of electro-optic
material may comprise a set of subtractive primary colors, for example cyan, magenta
and yellow pigments; it will readily be apparent that these colors may be distributed
among the first, second and third layers in any order. (Alternatively, the displays
of the present invention may use more than three primary colors, or use primary colors
that are not the conventional subtractive primary colors.) The layer containing the
yellow pigment may be arranged to have a smaller number of gray levels than the layers
containing the cyan and magenta pigments. In one form of the invention, the electro-optic
display has a viewing surface through which an observer views the display, and the
two electro-optic layers closest to the viewing surface contain cyan and yellow pigments,
in either order.
[0024] The charged particles in at least one of the layers (and preferably both the first
and second layers) may be movable between a first optical state, in which the pigment
particles occupy substantially the whole area of each pixel, and a second optical
state, in which the pigment particles occupy only a minor proportion of the area of
each pixel.
[0025] When the first and second electro-optic layers (and the third electro-optic layer
if present) are both electrophoretic layers, independent control of the pigments in
these layers may be facilitated by controlling a variety of physical parameters of
the two layers. For example, the yield stresses of the fluids in the first and second
layers may differ; the sizes of the microcavities in the first and second layers may
differ; the particles in the first and second layers may differ in at least one of
size, shape and electrical conductivity; or the fluids in the first and second layers
may differ in at least one of viscosity and electrical conductivity.
[0026] A preferred form of electro-optic display of the present invention has a viewing
surface at or adjacent the surface of the first electro-optic layer remote from the
second electro-optic layer, and has a third electro-optic layer on the opposed side
of the second electro-optic layer from the viewing surface, the third electro-optic
layer comprising first and second types of particles of differing colors disposed
in a fluid and capable of moving through the fluid on application of an electric field
to the third electro-optic layer, the first and second types of particles being of
differing electrophoretic mobility. The first type of particles in the third electro-optic
layer may be white. The particles in the first and second electro-optic layers may
be yellow and cyan, in either order, and the second type of particles in the third
electro-optic layer may be magenta.
[0027] At least one of the first and second electrodes in the electro-optic display of the
present invention may occupy only a minor proportion of the area of a pixel. In a
microcavity display of the present invention, the walls of the microcavity may have
a higher electrically conductivity than the phase comprising the plurality of charged
pigment particles dispersed in the fluid. One of the electro-optic layers may have
at least two stable states, while a second electro-optic layer may have only one stable
state.
[0028] Many such blends of organic pigments can be made to display a substantial color gamut.
By careful selection of the organic pigments used, the differently colored organic
pigments present can be chosen to have substantial different dielectrophoretic mobilities,
so that by manipulating the frequency and voltage applied to the electrophoretic medium,
each pigment individually can be made to be in a dispersed state or in a packed state,
i.e., the different organic pigments can be made to "shutter" independently of one
another. Having a particular organic pigment in its dispersed state allows that pigment
to absorb the corresponding color of transmitted light; the more uniform the dispersion,
the greater the absorption. On the other hand, having a particular organic pigment
in its packed state minimizes the fraction of the area of the electrophoretic medium
where that pigment is located, thus minimizing the absorption by that pigment. It
will readily be apparent by controlling the "shuttering" of differently colored particles
independently of one another, a substantial color gamut can be displayed.
[0029] Such a multi-colored VT medium can be used directly as a full color display; if a
reflective display is desired, a reflector can of course be placed behind the medium
(i.e., on the opposed side of the medium from that viewed by the user). Alternatively,
such a multi-colored VT medium can be used as a substitute for a conventional "static"
color filter array, and used in combination with a monochrome reflective medium (either
an inherently reflective medium or a transmissive medium provided with a reflector);
this monochrome medium need not be an electrophoretic medium but could be any known
type of electro-optic display. Such a dual layer display would have the advantage
of allowing the multi-colored VT medium to control only the color of the various pixels
or sub-pixels of the display, while the monochrome medium would control the brightly
of each pixel or sub-pixel. Requiring the multi-colored VT medium to control only
color lessens the demands upon independent control of the multiple pigments used in
the VT medium, since no longer is the VT medium required to provide all colors at
all levels of saturation.
Figure 1 of the accompanying drawings, as already mentioned, illustrates a simple
color cube.
Figure 2A is an idealized side elevation of a single layer of dried microcapsules
formed on a flat surface.
Figure 2B is a top plan view of the layer of microcapsules shown in Figure 2A.
Figure 2C is an idealized side elevation, similar to that of Figure 2A, of a double
layer of microcapsules formed on a flat surface.
Figure 2D is a top plan view of the double layer of microcapsules shown in Figure
2C.
Figure 3A is a schematic side elevation of two capsules in which pigment shuttering
is effected using concentrator electrodes.
Figure 3B is a schematic side elevation, similar to that of Figure 3A, of two capsules
which use side wall shuttering of pigment.
Figure 3C is a schematic side elevation, similar to those of Figures 3A and 3B, showing
how geometric pigment shuttering may be effected in a double layer of capsules similar
to that shown in Figures 2C and 2D.
Figures 3D and 3E show respectively the non-shuttered and shuttered states of the
second layer of capsules in a double layer of capsules similar to that shown in Figures
2C and 2D.
Figure 4 is a schematic cross-section through a single capsule used in a display of
the present invention and illustrates pigment dispersion effected by capsule wall
charging.
Figures 5A, 5B and 5C illustrate, in idealized form, three different ways in which
shuttered pigment particles may be packed in a microcavity, and the corresponding
transmission efficiency for a double pass of light through the microcavity.
Figure 6 is a graph showing the transmission efficiencies of the three pigment arrangements
of Figures 5A, 5B and 5C as a function of the volume fraction of pigment in the cavity.
Figures 7A, 7B and 7C, which are reproduced from Todd Squires and Martin Bazant, J. Fluid Mech., (2004) 509, 217-252, show in cross-section a spherical pigment particle surrounded by a solvent that
contains a charge control agent, and illustrates the forces acting on the pigment
particle in various types of applied electric fields.
Figures 8A-8D illustrate various states of a two electro-optic layer display of the
present invention, and show the manner in which two layers can be made to shutter
independently using a common waveform.
Figures 9A and 9B are projections on the a*b* plane of the La*b* color space and illustrate
the color changes occurring during the operation of one display of the present invention
in which two layers switch at the same rate.
Figures 10A and 10B are projections similar to those of Figures 9A and 9B respectively
but illustrate the color changes occurring in a display in which the two layers switch
at different rates.
Figure 11 is a schematic side elevation, similar to those of Figures 8A-8D but showing
a three-layer display of the present invention in which one layer contains no pigment
particles.
Figures 12A and 12B are schematic side elevations, similar to that of Figure 11, showing
two further three-layer displays of the present invention.
Figure 12C and 12D show two different states of a further three-layer display of the
present invention.
Figures 13A and 13B illustrate the color performance of the display tested in Example
10 below.
Figures 14A and 14B illustrate the color performance of the display tested in Example
11 below.
Figures 15A and 15B illustrate the color performance of the display tested in Example
12 below.
Figure 16 (which is similar to Figures 13B, 14B and 15B) illustrates the color performance
of the display tested in Example 13 below.
Figure 17 illustrates the colors obtained in Example 3 below.
[0030] As already mentioned, an electro-optic display comprises at least first and second
layers of electrophoretic material, each of which comprises a plurality of charged
particles dispersed in a fluid and capable of moving through the fluid on application
of an electrical field to the layer. The first layer of electrophoretic material is
capable of displaying at least one optical state which cannot be displayed by the
second layer. The display further comprises a first electrode disposed on one side
of the first and second layers, and a second electrode disposed on the opposed side
of the first and second layers from the first electrode; no electrode is present between
the first and second layers. Typically, the electrophoretic display will further comprise
a third layer of electrophoretic material comprising a plurality of charged particles
dispersed in a fluid and capable of moving through the fluid on application of an
electrical field to the layer. The third layer is capable of displaying at least one
optical state which cannot be displayed by the first and second layers. The second
electrode is disposed on the opposed side of the first, second and third layers from
the first electrode, and no electrode between the second and third layers, the single
pair (or set) of electrodes being used to control all three layers at least partially
independently of one another.
[0031] The basic concept behind the present invention is perhaps most easily appreciated
by considering a three-layer display such as that shown in Figure 12A of the accompanying
drawings. The electro-optic layer closest to the viewing surface (the surface through
which an observer views the display) has two different optical states, a "dispersed"
or "unshuttered" state in which color is present over the whole area of a pixel, and
a "concentrated" or "shuttered" optical state in which the color is absent from the
major proportion of the area of the pixel and is present (if at all) only in a minor
proportion of the area of the pixel. The second electro-optic layer (which lies behind
the first electro-optic layer, as seen by the observer) operates in a manner similar
to the first layer but uses a different color.
[0032] The third electro-optic layer (the one remote from the observer) of such a three-layer
display may operate in the same manner as the first and second electro-optic layers
using a third color; the first, second and third colors are normally chosen to form
a set of subtractive primaries. If the third layer does act in this manner, a reflector
will be positioned behind the display to reflect light which has passed through the
three electro-optic layers back through those layers to the observer. More commonly,
however, the third electro-optic layer is a chosen so that it can display either one
of two colors, namely the third subtractive primary or white; the third electro-optic
layer may be, for example, a conventional dual particle electrophoretic layer such
as described in many of the aforementioned E Ink patents and applications.
[0033] The three electro-optic layers of the display are disposed between a single set of
electrodes and an appropriate display controller is used to enable the three electro-optic
layers to be driven at least partially independently of one another. In a preferred
form of the display of the present invention in which the first and second electro-optic
layers are shutter mode electrophoretic layers and the third electro-optic layer is
a dual particle electrophoretic layer, the third layer can be driven using a direct
current driving method, while the first and second layers are driven by different
shuttering drive methods, as described in detail below.
[0034] Hereinafter for convenience, a material that selectively absorbs light is referred
to as a "pigment", which term should be interpreted to include dyes, photonic crystals,
etc., capable of selectively absorbing light. In embodiments of the invention intended
to provide full color imaging using three subtractive primary pigments, light will
typically be selectively filtered through at least two pigments before being reflected
back to the viewer. The third pigment may be transparent or reflective, as described
in more detail below. It is therefore necessary for at least two of the pigments used
in the present invention to be light-transmissive and not substantially back-scattering.
Thus, for example, a magenta pigment is intended to absorb green light but must pass
blue and red light to underlying layers. In regions where green light is not intended
to be absorbed, it is necessary that the pigment not be present in the optical path.
One way in which such removal of the pigment from the optical path may be achieved
is to concentrate the pigment in only a (minor) portion of the pixel area, thus reducing
its covering power. When magenta color is desired, the pigment is spread over the
whole pixel area to enable the maximum amount of light to be absorbed. The process
of spatially concentrating the pigment to reduce its areal covering power is referred
to as "shuttering" the pigment.
[0035] Numerous methods can be used for shuttering pigments in response to an applied electric
field, as described in detail below. As already mentioned, the displays of the present
invention may make use of electro-optic layer formed from microcapsules, which may
be coated in roll-to-roll processes. Alternatively, the electro-optic layers may use
microcells, microcups or wells such as are known in the art. Although the invention
will hereinafter primarily be described with regard to electro-optic layers using
microcapsules, it is believed that those skilled in the technology of electro-optic
displays will have no difficulty adapting the microcapsule based structures described
to other methods for spatially segregating the pigment containing phases.
[0036] As already indicated, the present invention is directed to electro-optic displays
in which multiple pigments are controlled by a single set of electrodes. Since the
electric fields present between a single set of electrodes are substantially the same
regardless of whether one or a plurality of electro-optic layers are present between
those electrodes, it will be appreciated that the reaction of various pigments to
the electric fields generated the single set of electrodes will in most cases be substantially
the same regardless of whether the pigments are present between the electrodes in
the same or different electro-optic layers. Accordingly, various embodiments of the
present invention can be produced depending upon whether various pigments are present
in the same or different electro-optic layers. Although the present invention will
primarily be described with reference to embodiments of the invention in which each
electro-optic layer (except one) contains only a single pigment, depending upon the
exact driving methods used, all the pigments used may be contained in a single layer,
or two pigments may be contained in one layer and a third in a different layer, and
the means used to shutter the pigments may differ in different layers. A description
is given below of one display of the present invention in which three pigments are
present in a single layer of capsules.
[0037] Certain "geometric" methods for shuttering pigments rely, in some cases, upon the
self-assembly of coated layers of microcapsules. Hence, a preliminary discussion of
such coated layers is desirable. As discussed in many of the aforementioned E Ink
patents and applications, and especially in United States Patents Nos.
6,067,185;
6,392,785;
7,109,968; and
7,391,555, in practice prepared by forming an emulsion in which the discontinuous phase comprises
droplets of an electrophoretic internal phase that comprises at least one pigment
and a fluid (which is typically a low polarity, substantially water-immiscible hydrocarbon),
normally with the addition of a charge control agent. The continuous phase of the
emulsion comprises an aqueous solution of a polymer, typically gelatin. Polymeric
material is deposited onto the surface of the droplets by, for example, formation
of a coacervate of the gelatin and a second polymer, typically acacia, to form a thin
capsule wall that may optionally be cross-linked, for example with an aldehyde. The
resultant deformable microcapsules are spheres of approximately 20-100 µm in diameter.
When such microcapsules are coated on a flat surface at a controlled coverage, they
form essentially a monolayer of capsules. When this monolayer is dried, the capsules
tend to contract vertically (i.e., perpendicular to the surface on which they are
coated) and expand laterally to form oblate spheroids. Eventually, as the capsules
expand laterally, their sidewalls come into contact with each other , and the capsules
deform into polyhedral prisms whose shapes are similar to those formed by cells in
foams. Ideally, a single layer of capsules will form a "honeycomb" (a two dimensional
hexagonal lattice) of hexagonal prisms whose side walls, viewed in projection, meet
at 120 degree angles, as shown (in idealized form) in Fig. 2A. (In practice, the microcapsules
vary somewhat in size, and photomicrographs of dried single microcapsule layers typically
show honeycombs similar to that illustrated in Figure 2B, but with each microcapsule
having from 4 to 8 neighbors. For reasons which will appear below, shuttering of pigments
in the displays of the present invention is not greatly affected by such deviations
from an ideal honeycomb of Figure 2B.) Also, as shown in Figure 2A, typically the
faces of the capsules, that are in contact with the planar substrate onto which the
capsules are coated, will conform to the flat surface, while the exposed face of each
capsule will adopt a curved, "domed" shape.
[0038] When a second layer of microcapsules is coated on top of the first layer, surface
tension forces leading to minimization of surface energy tend to cause deformation
of the domed upper surfaces of the capsules in the first layer into a foam-like geometry
as illustrated schematically in Fig 2C. In this geometry, the upper portion of each
capsule in the first layer has a substantially pyramidal shape in which the pyramidal
portion are substantially flat and the intervening edges are substantially straight
lines, four of which meet at each vertex at the tetrahedral angle of 109.5 degrees.
For a detailed description of the geometry of foams, see for example "
Foams: Theory, Measurements, and Applications", R. K. Prud'homme and S. A. Khan, eds.,
Marcel Dekker, Inc., 1996. Classically, the shape of each cell in a monodispersed foam is a semi-regular solid
(essentially a truncated octahedron) with 14 faces. Note that the lower portions of
each capsule in the second layer also has a substantially pyramidal shape, so that
the pyramidal portions of the first and second layers fit together with the lowest
vertex of each pyramidal section in the second layer filling into the recess between
three pyramidal sections in the second layer. As explained below, the pyramidal sections
of such double layers of capsules are important in one type of pigment shuttering.
It will be appreciated that if a third layer of capsules is coated over the second
layer, the interface between the second and third layers will display the same type
of interpenetrating pyramidal sections as the interface between the first and second
layers.
[0039] Figures 3A-3E illustrate various forms of pigment shuttering which may be employed
in the displays of the present invention. Figure 3A illustrates the shuttered optical
state of a display which uses concentrator electrodes 102. Such concentrator electrodes
are small electrodes which occupy only a small fraction of the area of each pixel
so that when an appropriate voltage is applied to the concentrator electrodes, the
pigment is attracted to the concentrator electrodes and thus only occupies a small
fraction of the area of each pixel, i.e., the pigment is shuttered.
[0040] Concentrator electrodes may be patterned electrodes by which the display is addressed,
for example grids of conductive material such as silver or gold that may be patterned
onto a substrate by printing or lithographic methods, or continuous conductors that
are masked with patterns of dielectric material. Concentrator electrodes may also
be individually-addressable electrodes that are associated with an array of thin-film
transistors. Alternatively, discrete, isolated conductive particles that are not directly
electrically-addressed may be incorporated into a layer or layers within the display.
[0041] Figure 3B illustrates geometric /capsule wall pigment shuttering in the first layer
of a double capsule layer of the type illustrated in Figures 2C and 2D. Because of
the pyramidal form of the upper section (as illustrated) of the first layer of capsules,
when the potentials applied to electrodes 104 and 106 are arranged so that the pigment
particles are attracted towards electrode 104, the pyramidal form of the upper sections
of the capsules in the first layer will cause the pigment to form pigment packs 108
which occupy only the area around the uppermost vertex of each pyramidal section,
and thus occupy only a small fraction of the area of each pixel, i.e., the pigment
is shuttered.
[0042] Geometrical/capsule wall shuttering can be achieved naturally by the use of more
than one layer of capsules whose wall materials are more electrically conductive than
their internal phase. For example, a gelatin capsule wall typically has a conductivity
on the order of 10
-7 S/m (although this value is strongly dependent upon the degree of hydration of the
polymeric material comprising the capsule wall). An electrophoretic internal phase
typically has a conductivity much less that this, on the order of 10
-8 S/m. Thus, the capsule wall of one layer of capsules can act as a concentrator "electrode"
for a second layer of capsules. In addition, a geometrical shutter may be provided
by the pyramidal shape that may be adopted by the capsule, as described above. If
needed, geometrical shutters may be achieved by templated coating of capsules into,
for example, V-shaped grooves as described in United States Patents Nos.
6,130,774 and
6,172,798. Geometrical shutters may also be fabricated using photolithographic or embossing
methods, or other methods that are well-known in the art.
[0043] Figures 3D and 3E illustrate the use of geometric shuttering in the second layer
of a double capsule layer of the type illustrated in Figures 2C and 2D. As shown in
Figure 3D, when the potentials applied to electrodes 104 and 106 are arranged so that
the pigment particles are attracted towards electrode 104, because of the domed shaped
of the upper portions of the second layer of capsules, the pigment spreads out over
the whole area of the domed portion, and thus the entire pixel area, and is not shuttered.
On the other hand, when the potentials applied to electrodes 104 and 106 are arranged
so that the pigment particles are attracted towards electrode 106, the pyramidal form
of the lower sections of the second layer of capsules causes the pigment to form small
pigment packs 110 adjacent the lowermost vertex of each pyramidal section, and thus
occupy only a small fraction of the area of each pixel, i.e., the pigment is shuttered.
[0044] Figure 3C illustrates side wall shuttering. In this form of shuttering, in the shuttered
state the pigment is moved laterally parallel to the plane of the electrodes so that
it forms pigment 112 adjacent the side walls of the capsules.
[0045] Other methods for shuttering, such as use of anisotropic particles, for example,
needles or plates that may be oriented with their principal axes either perpendicular
or parallel to the plane of the display, or color-changing pigments, or swelling and
deswelling of gels, or other similar methods that are known in the art, may also be
used in the displays of the present invention.
[0046] As will readily been seen from the discussion of Figures 3A, 3B, 3D and 3E above,
pigment shuttering using concentrator electrodes or geometrical/capsule wall shuttering
may be achieved with direct current addressing of a display, in which the pigment
motion is in the direction of the applied electric field. Side-wall shuttering may
be achieved by addressing the display with alternating, in which case net pigment
motion may be in a direction perpendicular to the applied electric field, as described
in more detail below, such that pigment in the interior of the capsule is deposited
in an equatorial "belt" around the capsule.
[0047] The displays of the present invention obviously require some method for dispersing
the pigment from its shuttered state to its unshuttered state, in which the pigment
occupies substantially the entire area of a pixel. One method for such pigment dispersion
that is especially preferred for use in conjunction with concentrator electrode or
geometrical/capsule wall shuttering is illustrated schematically in Figure 4, which
illustrates the use of a combination of DC-addressing and a charged capsule wall being
used to move a pigment perpendicular to an applied electric field. In the capsule
shown in Figure 4, the loading of pigment is very low (around 1% of the volume of
the capsule) such that it may be concentrated into a very small region (shown as the
lowermost vertex of the lower pyramidal section of the capsule in Figure 4). Upon
application of an electric field, the pigment would normally migrate from this vertex
to the opposed vertex (i.e., vertically upwardly as illustrated in Figure 4), where
it would again be concentrated in a very small region adjacent the uppermost vertex
of the upper pyramidal section of the capsule. By providing an attractive force between
the pigment particles and the capsule wall, a perpendicular component (i.e., a component
horizontally as illustrated in Figure) may be added to the electrical force applied
to the particles, and so that the particles spread out laterally from the small region
they occupy in their shuttered position. The necessary attractive force may be electrostatic.
Thus, in some embodiments of the present invention, it is preferred that the pigment
particles and the capsule wall bear charges of opposite polarity. (Obviously, this
aspect o the invention cannot generally be applied to capsules which contain particles
bearing charge of both polarities, and is best suited to capsules containing only
one type of particle or "same polarity dual particle capsules, as described for example
in United States Patent No.
6,870,661) For example, if gelatin/acacia is used to form the capsule wall, and a charging
agent such as Solsperse 17000 (available from Lubrizol) is used, the capsule wall
may attain a negative charge and a pigment that attains a positive charge with the
same charging agent is preferred. Other methods that may provide attraction between
the pigment particles and the capsule wall include the use of flocculating agents,
especially depletion flocculants. The result of using such capsule-wall attraction
is that the pigment will be essentially invisible at either extreme of a DC pulse,
but visible during the transition from one concentrated state (at the top of the capsule)
to another concentrated state (at the bottom of the capsule) or
vice versa. The pigment may be trapped in what would be a transient state in simple DC driving
by driving with AC having a frequency of between about 30 and 50 Hz, and applying
a DC offset to the AC drive.
[0048] The present invention is not confined to use of a mobile charged pigment with a capsule
wall bearing a charge of the opposite polarity but extends to the use of such a pigment
with any fixed surface bearing a charge of the opposite polarity. The fixed surface
acts to constrain the motion of the pigment in an applied field. The medium containing
the pigment and the surface need not be encapsulated.
[0049] The shuttering mechanisms described above may be combined with conventional switching
of pigments using DC addressing to give rise to particle motion within a capsule parallel
to the applied field as already mentioned with regard to Figures 3D and 3E. In this
case is may be desirable that geometrical/capsule wall shuttering not occur, and this
can be ensured by incorporating more pigment into the capsule than can be concentrated
in a groove or crevice. Such conventional electrophoretic switching may involve a
single pigment moving through a dyed liquid, dual pigments of the same or opposite
charge, or combinations of multiple pigments and dyed fluids, as described in the
aforementioned E Ink patents and applications.
[0050] Shuttering methods of all types tend to impose limitations on the volume fraction
of pigments particles which can be present in an electrophoretic medium. It is desirable
that at least about 85 per cent of light be transmitted through a layer of shuttered
pigment in a single pass, i.e., the pigment should not absorb more than about 15 per
cent of the light; this corresponds to a reflection efficiency of about 70 per cent
for a double pass through the shuttered layer such as will normally occur in the displays
of the present invention. Figures 5A, 5B and 5C show, in simplified form, three different
possible forms of packing of pigment particles using some idealized shuttering methods.
In the following simplified analysis, light losses due to (
inter alia) total internal reflection, scattering except by a Lambertian reflector behind the
cavity, and interfacial reflections are ignored. Fig. 5A pigment is deposited onto
the side-walls of a cavity whose walls are perpendicular to the plane of the display.
Assuming that the pigment absorbs all incident light and that light passes once through
the cavity, is reflected in a Lambertian fashion, and then passes a second time through
the cavity, the proportion of light absorbed is (1-α)
2 where α is the volume fraction of the pigment within the cavity. In Figure 5B, the
pigment is collected in a half-cylinder on one face of the cavity parallel to the
viewing surface of the display (which is assumed to be horizontal in Figures 5A-5C).
The form of pigment collection will typically be appropriate for collection at a concentrator
electrode in the absence of any geometrical shuttering. Figure 5C shows concentration
of pigment into a spherical shape.
[0051] Figure 6 is a graph showing the estimated double pass transmission efficiency for
each shuttering geometry shown in Figures 5A, 5B and 5C as a function of the volume
fraction of the pigment within the cavity. Assuming that a double pass efficiency
of 70 per cent is acceptable, Figure 6 shows that this requires not more than about
1 per cent by volume of pigment for a hemicylindrical pigment geometry (Figure 5B),
and not more than about 5 per cent by volume for a spherical pigment geometry (Figure
5C). In view of these low acceptable pigments concentrations ("loadings") it is preferred
that pigments used for shuttering have the maximum possible extinction coefficient
so that they can be used in the least possible loading.
[0052] Such volume fraction limitations for shuttered pigments also imposes constraints
on the preferred particle size of such pigments. Particles that are randomly arranged
on a surface cover that surface less efficiently than an ordered, close-packed monolayer,
such that approximately two monolayer-equivalents of particles are required for an
area coverage of 90 per cent. In addition, for a typical dye having an extinction
coefficient of 50,000 L/mole/cm, a specific gravity of 1.5 and a molecular weight
of 500, a perfectly-packed layer of 70 nm thickness is required for an optical density
of 1 (i.e., 90 per cent absorption of light). It is therefore preferred that for such
a dye, the diameter of the pigment particle be on the order of half this thickness
or less. In practice, pigment particle sizes of less than about 100 nm diameter are
preferred for concentrator electrode and geometrical/capsule wall shuttering. Larger
particles may be hidden using side-wall shuttering since this method permits a larger
loading of pigment for the same degree of shuttering, as described above.
[0053] Additional optical losses may occur if the positions at which the pigments are shuttered
in separate layers do not overlie one another (i.e., are not registered, as would
be the case when the pigments are located in different layers in a display having
multiple layers of capsules). If the absorption spectra of the pigments overlap, some
light of a wavelength absorbed by both pigments may be absorbed in one area of a pixel
by a first shuttered pigment in a first layer and in another area of the same pixel
by a second shuttered pigment in a second layer. This problem can be avoided by removing
spectral overlap in the shuttering pigments so that there is no wavelength absorbed
by two pigments. Thus, in a display when two pigments are shuttered and a third is
switched by conventional electrophoresis, it is preferred that the two shuttered pigments
be yellow and cyan (whose absorption spectra are both designed to pass green light,
and which therefore do not significantly overlap).
[0054] As mentioned above, AC addressing may be used to shutter pigments. A rich variety
of phenomena occur when AC addressing is employed, including induced-charge electro-osmosis
and electrophoresis and induced-dipole effects such as dielectrophoresis and particle
chaining. Which behavior occurs is affected by the field strength and frequency applied
and by properties of the components in the capsule internal phase, as will now be
described in more detail.
[0055] Figure 7A shows a schematic cross-section through a spherical pigment particle surrounded
by a solvent that contains a charge control agent (CCA). The CCA is typically a surfactant-like
molecule comprising ionic groupings, hereinafter referred to as "head groups". At
least one of the positive or negative ionic head groups is preferably attached to
a non-polar chain (typically a hydrocarbon chain) that is hereinafter referred to
as a "tail group". It is thought that the CCA forms reverse micelles in the internal
phase and that a small population of charged reverse micelles leads to electrical
conductivity in the internal phase. The CCA also is thought to adsorb onto the surfaces
of the pigment particles and onto the interior walls of the capsules. Collectively
the CCA and the reverse micelles mediate charging of all surfaces (on the particle
and the capsule wall) in the internal phase of the electrophoretic medium.
[0056] It is thought that a particle with immobilized charge on its surface sets up an electrical
double layer of opposite charge in the surrounding fluid. Ionic head groups of the
CCA may be ion-paired with charged groups on the particle surface, forming a Stern
layer of immobilized charged species. Outside this layer is a diffuse layer comprising
charged micellar aggregates of CCA. In conventional DC electrophoresis an applied
electric field exerts a force on the fixed surface charges and an opposite force on
the mobile countercharges, such that slippage occurs within the diffuse layer and
the particle moves relative to the fluid. The electric potential at the slip plane
is known as the zeta potential.
[0057] Induced-charge electro-osmosis (hereinafter abbreviated "ICEO", but known as "AC
electro-osmosis") is a similar phenomenon but occurs in response to induced charge
rather than fixed surface charges. It is described in
V A. Murtsovkin, Colloid J., 58, 341-349 (1996) and in a series of papers by H. Morgan and co-workers (see, for example,
J. Colloid Interface Sci., 217, 420-422 (1999) and
Phys. Rev. E, 61, 4011-4018 (2000)), and has more recently been reviewed in detail by Squires and Bazant (
J. Fluid Mech., 509, 217-252 (2004). In ICEO, an externally applied electrical field induces a polarization in the vicinity
of a surface and simultaneously drives the resulting electro-osmotic flow. This creates
a flow velocity that is nonlinear in the applied field strength. In the presence of
an applied electric field an induced dipole may be set up (see Figure 7A), the magnitude
of which depends upon particle bulk and surface properties including conductivity,
dielectric constant, size and shape. This induced dipole in turn causes a flow of
ionic species (probably micelles) in the fluid that sets up a corresponding double
layer of opposite charge (Figure 7B). An electro-osmotic flow is then driven (Figure
7C) such that the fluid is drawn in from the poles and expelled at the equator. The
direction of the fluid flow is the same irrespective of the polarity of the applied
electric field, and the flow can thus be driven by an applied AC potential. In the
case of a spherical particle in a uniform field, no particle motion would result (since
the flows are symmetrical). In practice, however, pigment particles are not perfectly
spherically symmetrical and jets of the mobile phase may be set up that induce chaotic
motion of the particles.
[0058] Bazant has estimated the charging time for establishment of the double layer (Figure
7B) as:

[0059] for a conductive cylinder in an electric field, where
λD is the Debye length
, a is the particle radius, and D the diffusion constant of the charge carrier in the
mobile phase. Although pigment particles are typically composed of dielectric materials,
electrical conduction within the Stern layer may occur through a number of known mechanisms,
including proton hopping (particularly in the presence of adsorbed water) and therefore
the assumption of conductivity is not unreasonable in the present context. The following
discussion is included in order to provide a qualitative, heuristic picture of some
of the mechanisms that may occur in the present displays and does not in any way limit
the scope of the invention.
[0060] Equation (1) above shows that the charging time gets longer as the particle gets
larger. The maximum induced-charge electro-osmotic velocity is then estimated as:

where E is the magnitude of the applied field,
ω the angular frequency and
η the viscosity of the mobile phase. It can be seen that as the frequency increases
the maximum induced-charge electro-osmotic velocity decreases. At high frequencies,
where ω
2τ
c2 »1, the induced-charge electro-osmotic velocity becomes very low (because there is
no time to charge up the double layer) and screening of the induced dipole by the
charge carriers in the fluid is reduced. At such frequencies particle-particle interactions
leading to chaining, or interactions with field gradients leading to dielectrophoretic
mobility, may occur. Thus, applying an AC field with increasing frequency may at low
frequencies cause electro-osmotic flow, as described above, but as the frequency is
increased particle-particle interactions and dielectrophoresis may dominate. The result
may be, for example, that all the particles concentrate by induced-dipole aggregation.
They are most likely to concentrate in regions where, at the electro-osmotic driving
frequency, stationary points of the flow may be located (i.e., in a ring around the
equator in the case of particles within a spherical capsule). The frequency at which
particle concentration occurs (in the idealized case) is proportional to the applied
field and also depends inversely upon the particle size, since:

[0061] The present inventors have observed that when a display is addressed at relatively
low AC frequencies (typically in the range of 30-100 Hz) encapsulated pigment particles
exhibit high-speed motion and become uniformly distributed in a capsule. At higher
frequencies the pigment particles' motion slows down and they may collect at the capsule
walls, leading to transparency (shuttering). If the frequency is suddenly increased
from a relatively low to a relatively high value, however, there may not be time for
the particles to reach the stationary points of flow at the wall, and they will become
immobilized but not shuttered. Thus, for optimal shuttering it is preferred that either
the frequency be ramped from a low to a high value at constant voltage, or that the
voltage be ramped from a high to a low value at constant frequency, or some combination
of these two ramps.
[0062] The frequency at which the transition from ICEO motion to a stationary state occurs
is related to (and in some cases proportional to) the applied voltage and depends
upon particle properties such as size, shape and conductivity and to fluid properties
such as viscosity, conductivity and dielectric constant. Thus, pigments may be selectively
and independently addressed by varying the frequency of AC used to drive a display.
For example, a first pigment in a first capsule may have a large size and be incorporated
into a fluid of high viscosity, whereas a second pigment in a second capsule layer
may have a small size and be incorporated into a fluid of low viscosity. At a lowest
addressing frequency ω
1, both pigments will be distributed and spread out by electro-osmotic motion. At a
higher addressing frequency ω
2 the first pigment may be shuttered while the second pigment is still in motion. At
a yet higher frequency ω
3 both pigments may be shuttered. If the frequency is suddenly switched from ω
1 to ω
3 (or to a frequency slightly lower than ω
3 and then increased to ω
3) there may not be time for the first pigment to shutter but there may be time for
the second pigment to do so. Thus, using a constant voltage and varying only the frequency
of addressing, it is possible to access different colors while driving each color
with the same waveform. It will be clear that the same effect may be obtained by holding
the frequency constant and varying the voltage, and that such a scheme may be extended
to more than two colors. Examples 1-3 below describe addressing more than one color
in a single capsule layer using alternating voltages of different frequencies. (It
will of course be apparent that, when the frequency at which the transition from ICEO
motion to a stationary state occurs for different particles is controlled by particle
properties alone it is possible to incorporate particles of more than one color into
a common capsule rather than providing a separate environment for each pigment, as
described above.)
[0063] Another method for using shuttering a plurality of pigments while driving all pigments
with a common waveform is illustrated in Figures 8A-8D, which show in schematic cross-section
a two layer display of the present invention having a first layer of microcapsules
containing a first pigment coated onto a substrate bearing a concentrator electrode
such as a grid electrode, over which is coated a second layer of capsules containing
two oppositely-charged pigments, one of which is (the second pigment) is colored and
the other of which is white. (It should be noted that the display shown in Figures
8A-8D is intended to be viewed
from below as illustrated.) Addressing of the two colors (to the four possible extreme states
of color 1, color 2, color 1 plus color 2, and no color) is achieved by taking advantage
of differences between the timing of shuttering in the first layer and the timing
of vertical switching in the second layer. Figures 8A-8D illustrate four different
states of the display. In Figure 8A, the first pigment 802 is shuttered to the concentrator
electrodes 804 and the second pigment 806 is visible in front of the white pigment
808. In Figure 8B, the pigment 802 is spread uniformly across the first layer, while
the second layer is in the same state as in Figure 8A, so that the display shows the
first and second pigments 802 and 806 together against a white background. In Figure
8C, the second pigment 806 is hidden behind the white pigment 808 and the first pigment
is shuttered by being concentrated at the uppermost vertices of the upper pyramidal
sections of the first layer of capsules, so that the display shows the white pigment.
In Figure 8D, the first pigment 802 is spread uniformly over the upper surfaces of
the first layer of capsules, while the second layer is in the same state as in Figure
8C, so that the display shows the first pigment against on a white background. A display
of this kind is described in detail in Example 4, below.
[0064] The necessary independent control of the two capsule layers in Figures 8A-8D may
be achieved by exploiting differences in the rate of switching between the two types
of capsule. Such differences in rate can be non-linear with applied voltage if, for
example, the fluid within a capsule exhibits a yield stress, such that with an applied
voltage below a threshold value no pigment motion occurs within the capsule. Thus,
for example, if the first layer of capsules shown in Figures 8A-8D above have a voltage
threshold for switching of V1 and the second layer of capsules have a voltage threshold
of V2, where V2 > V1, the second layer could be addressed at a voltage greater than
V2 (which will also switch the first layer) after which the first layer could be switched
at a voltage V1 between V1 and V2 (without affecting the second layer). Such a scheme
can be extended to three layers of capsules having three voltage thresholds.
[0065] The necessary voltage thresholds may be provided in a variety of ways. As mentioned
above, the internal phase of a microcapsule may have a yield stress. Particles of
opposite charge to the shuttering pigment may be added to the capsule to create a
Coulombic threshold. These particles of opposite charge may be substantially non-scattering
and non-absorbing, such that they do not affect the absorption of light by the colored
pigment and do not affect the overall appearance of the display, being incorporated
simply to modulate the switching behavior of the interior of the capsule.
[0066] Another technique to address capsule layers independently is to make one layer of
capsules multi-stable (i.e., to endow this layer with image hysteresis, as may be
achieved by providing a polymer dispersed in the fluid - see United States Patent
No.
7,170,670, and to make a second layer that does not exhibit hysteresis and reverts to a default
state when not actively addressed. Figures 9A and 9B illustrate the color changes
of such a display in terms of their projection on the a*/b* plane of the La*b* color
space. Arrow i in Figure 9A represents switching from cyan to white, such as could
occur in the first layer of capsules in Figures 8A-8D. When a field of either polarity
is applied, the pigment shutters from a dispersed state, and, if it is assumed that
the image so formed is not stable, when the field is removed the shuttered pigment
redisperses and the default cyan state is re-formed. Arrow (ii) shows the switching
of white to yellow, such as could occur in the second layer of capsules shown in Figures
8A-8D. This switching is hysteretic, such that the final state is stable until the
field direction is reversed.
[0067] Figure 9B illustrates how four colored states can be achieved in this display when
the switching speeds of capsules in the first and second layers are the same. Arrow
(1) shows the display being driven by application of an electric field such that the
first layer of capsules is driven to white (from the default cyan state) and the second
layer is driven from white to yellow. Arrow (2) shows that as the driving field is
reduced to zero the second layer remains in the yellow state but the first layer defaults
to cyan, resulting in the combination of yellow and cyan, which is green. Arrow (3)
shows that as the display is then driven with an electric field of the opposite polarity
the first layer is again driven to white, while the second layer is driven from yellow
to white. The result is a white image. Finally, arrow (4) shows that as the field
is reduced to zero from the reversed polarity drive, the second layer remains white
while the first layer reverts to cyan, resulting in a cyan image. Different levels
of the colors may be attained by changing the time of driving at a particular voltage
(pulse-width modulation) or by changing the drive voltage.
[0068] A larger color gamut may be achieved if the rates of switching of the two layers
are not the same. Figures 10A and 10B are projections similar to Figures 9A and 9B
respectively but show the color changes occurring when the cyan shuttering layer is
faster than the white/yellow layer but not so fast that cyan can be completely shuttered
without any switching of the yellow layer. It is assumed that the white/yellow layer
exhibits hysteretic image stability whereas the cyan shutter does not (although similar
principles apply if both layers exhibit hysteretic image stability). In Figure 10A
there is seen the path that is followed as the white layer is switched to yellow.
At short times of switching the cyan layer is completely shuttered whereas the white
layer has not completely switched to yellow. This provides a mid-yellow state shown
as x in Figure 10A. Relaxation of the cyan shutter provides a blue-green color shown
as y. Continued switching of the yellow provides a completely yellow state, from which
green is obtained by relaxation of the cyan shutter. As is shown in Figure 10B, the
path followed when switching from yellow to white is not the same, although it visits
the same points at the extremes (i.e., open and closed) of the cyan shutter. It is
noteworthy that the pure yellow and white states are only attained with one direction
of driving. If the cyan shutter does not exhibit hysteretic image stability, a holding
voltage is required to maintain a state which is not the default.
[0069] Figure 11 shows a schematic side elevation of a three-layer display of the present
invention. This three-layer display is generally similar to the two-layer display
shown in Figures 8A-8D, except that the concentrator electrodes are replaced by a
first layer of capsules whose walls are more conductive than their interior. This
layer of capsules may contain no pigment and be transparent, serving simply to act
as a template and shape the second layer of capsules (containing the first pigment)
and provide a capsule wall shutter. The mechanism by which the display of Figure 11
achieves the four possible extreme states of two primary colors is exactly analogous
to that described above with reference to Figures 8A-8D. A three-layer display of
this kind is described in detail in Example 5 below.
[0070] A third primary color may be provided in the displays shown in Figures 8A-8D and
11 in several different ways. Figure 12A illustrates provision of a third primary
color that is shuttered using any of the three methods mentioned above (a concentrator
electrode is shown, but capsule wall/geometrical shuttering or side-wall shuttering
may be used also).
[0071] Figure 12B illustrates provision of a third color in the same layer as the second
color, i.e., in combination with a white pigment, and switched vertically. Again,
the third color should be switched considerably more slowly than either the first
or the second colors. In the display of Figure 12B, the second and third colors are
arranged side-by-side, which is a less favorable configuration that shown in Figure
12A. It is possible, however, for the capsules containing the third color to be of
a different size from those containing the second color, and that therefore some overlap
of the capsules may be achieved. In addition, some mixing of the second and third
colors may be achieved by light scattering within the structure. Fig. 12B shows a
capsule wall/geometrical shutter for the first pigment, but a layer of capsules may
be eliminated and concentrator electrodes used instead to shutter the first pigment.
[0072] Figures 12C and 12D show two different optical states of a three-layer display of
the present invention generally similar to the displays shown in Figures 12A and 12B.
In the display shown in Figures 12C and 12D, the first electro-optic layer (the lowest
layer as illustrated in Figures 12C and 12D) contains a yellow pigment, is state-stable,
has a threshold and requires a high operating voltage. The yellow pigment in this
layer is movable between the shuttered state shown in Figure 12C, in which the pigment
is confined to the uppermost vertex of the pyramidal upper section of each capsule
in this layer, and the unshuttered state shown in Figure 12D, in which the yellow
pigment covers the whole of the flat lower surface of each capsule. The second electro-optic
layer of the display shown in Figures 12C and 12D contains a cyan pigment and is not
state-stable. The cyan pigment in this layer can be moved between the two shuttered
positions shown in Figures 12C and 12D, in which the pigment is confined to the uppermost
and lowermost vertices of each capsule, and an unshuttered position (not shown) in
which the pigment is distributed uniformly throughout each capsule. The third electro-optic
layer of the display contains a magenta pigment which can be moved vertically (as
illustrated) between the unshuttered position shown in Figure 12C and the shuttered
position shown in Figure 12D. The upper electrode shown in Figures 12C and 12D is
provided with a white reflector.
[0073] As already indicated, in one aspect the present invention provides a variable transmission
electrophoretic medium comprising a plurality of different organic pigments in a fluid,
such that when all the pigments are dispersed substantially uniformly through the
fluid, the medium appears substantially black. Also, the medium is substantially free
from polymeric additives in the fluid (other than charge control or similar agents,
and surfactants) but still has a high degree of image stability. In a preferred form
of such a variable transmission medium, the pigments are chosen to have substantial
different dielectrophoretic mobilities, so that by manipulating the frequency and
voltage applied to the electrophoretic medium, each pigment individually can be made
to be in a dispersed state or in a packed state, and the medium can display a substantial
color gamut.
[0074] As is well known to those skilled in the pigment art, a blend of two or more color
pigments can be made to provide additional colors, including black. A broad range
of color pigments has been developed for demanding applications such as automotive
paints, and some of these pigments have demonstrated suitable properties for VT media.
Pigments of the quinacridone and phthalocyanine families have been found useful. Such
pigments can be blended to yield in total a very broad color gamut, but the added
constraint of requiring black to be part of the gamut has hitherto diminished the
color gamut achievable in a single medium.
[0075] Somewhat unexpectedly, it has been found that that some of the pigments useful in
VT media have been found to display a wide range of electrophoretic mobilities in
the sense of differing responses to a wide range of applied frequencies and voltages.
Accordingly, by manipulating the frequency and voltage applied to the electrophoretic
medium, each pigment individually can be made to be in a dispersed state or in a packed
state, i.e., the different organic pigments can be made to "shutter" independently
of one another. The dispersed state allows the pigment to absorb the transmitted light,
the more uniform the dispersion, the better the absorption. The packed state minimizes
the areal fraction of the medium where the pigment is located, thereby minimizing
the absorption by that pigment. If all the pigments are packed, then the medium will
assume its "open" or substantially transparent optical state. If, on the other hand,
all the pigments are dispersed throughout the fluid, the medium will assume a substantially
black optical state, provided with amounts and colors of the various pigments are
balanced to achieve a neutral color. If at least one pigment is dispersed and at least
one pigment is packed, the color of the medium will approach the color of the dispersed
pigment, and by independent control of the state of dispersion of the various pigments,
a substantial gamut of colors can be produced; for reasons which will be familiar
to those skilled in the color imaging art, it is normally preferred that such a VT
medium contain at least three different pigments having differing colors and dielectrophoretic
mobilities.
[0076] The displays of the present invention can, as already discussed, make use of various
driving methods to drive three separate pigments (whether those pigments be present
in one, two or three separate electro-optic layers). Perhaps surprisingly, it is possible
to drive three separate pigments substantially independently of one another using
only a single set of electrodes and DC voltages. Conceptually, the methods for driving
three different pigments using only DC and a single set of electrodes, may be summarized
as follows:
[0077] Assume that there are three color-forming layers (although the principle does not
require layers) with the following properties:
(a) Layer 1 has a voltage (or impulse) threshold, is state stable, and its color depends
upon the polarity of the applied voltage;
(b) Layer 2 has either a lower threshold or no threshold, is state stable, and its
color depends upon the polarity of the applied voltage; and
(c) Layer 3 has no threshold, is not state stable, and switches faster than layer
2. Layer 3 reaches the same state whether driven with a positive or a negative impulse and relaxes to its opposite
extreme when no potential is applied.
[0078] Given these three conditions, the drive scheme is:
(a) Use a high voltage to set layer 1 to the desired color. In practice, this could
be binary and in this case should be yellow. This will also affect layers 2 and 3.
(b) Use a lower voltage to set layer 2 to the desired color. This will not affect
layer 1, and will switch layer 3 to its extreme state.
(c) Allow layer 3 to relax to its desired color and keep it there with a holding voltage
(or pulses at any voltage).
[0079] The alternative to this, if all three layers are state stable, is the more straightforward
scheme of addressing sequentially at three different voltages for the three colors
and correcting the collateral switching of the faster layers when addressing the slower
ones. In this case the slowest layer is addressed first, and layers 1 and 2 each have
a threshold. However, this is much harder to engineer.
[0080] The following Examples are now given, though by way of illustration only, to show
details of preferred reagents, conditions and techniques used in the media of the
present invention.
Example 1 : First Medium containing Red, Green and Blue Pigments
[0081] The pigments used in this Example were:
Clariant Hostaperm Pink E 02, a red quinacridone pigment (available commercially from
Clariant Corporation, 4000 Monroe Road, Charlotte NC 28205), stated by the manufacturer
to have a specific gravity of 1.45, a surface area of 77 m2/g, and an average particle size of 90 nm;
Clariant Hostaperm Green GNX, a green copper phthalocyanine pigment from the same
manufacturer, and stated by the manufacturer to have a specific gravity of 2.05, a
surface area of 40 m2/g, and an average particle size of 50 nm; and
Clariant Hostaperm Blue B2G-D, a blue copper phthalocyanine pigment from the same
manufacturer, and stated by the manufacturer to have a specific gravity of 1.6, a
surface area of 44 m2/g, and an average particle size of 75 nm.
[0082] Millbases of each pigment containing approximately 20 per cent by weight of the pigment
in d-limonene and 0.0044 g of Solsperse 17000 per square meter of pigment surface
area (as stated by the manufacturer) were prepared substantially as described in the
aforementioned 2007/0146310. Samples of each millbase were diluted to 0.01 weight
per cent pigment with d-limonene and the resultant dispersion measured for color transmission
with a Minolta CM-3600d spectrometer using 2 mm path length sample cuvettes. The millbases
were also blended to produce a mixed dispersion having a color as close to black as
possible (i.e., having the smallest possible a* and b* values in the conventional
CIE L*a*b* color space). The results are shown in Table 1 below.
Table 1
| Color (saturated) |
L* |
a* |
b* |
%R |
%G |
%B |
| Red |
37.1 |
55.7 |
-17.4 |
100 |
0 |
0 |
| Green |
21.1 |
10.1 |
-28.5 |
0 |
100 |
0 |
| Blue |
22.2 |
22.6 |
-17.6 |
0 |
0 |
100 |
| Black |
31.0 |
0 |
-17.1 |
43.2 |
0 |
56.8 |
Note that the "black" blend actually tended to green even without adding any green
pigment; this was caused by the blue-green hue of the "blue" pigment.
Example 2 : Second Medium containing Red, Green and Blue Pigments
[0083] Example 1 was repeated except that Clariant Ink Jet Magenta E02 VP 2621, a quinacridone
pigment having an average particle size of 70 nm, was substituted for the pink pigment
used in Example 1. Again, the millbases were also blended to produce a mixed dispersion
having a color as close to black as possible. The results are shown in Table 2 below.
Table 2
| Color (saturated) |
L* |
a* |
b* |
%R |
%G |
%B |
| Red |
39.6 |
45.6 |
-17.6 |
100 |
0 |
0 |
| Green |
21.1 |
10.1 |
-28.5 |
0 |
100 |
0 |
| Blue |
22.2 |
22.6 |
-17.6 |
0 |
0 |
100 |
| Black |
31.0 |
0 |
-16.9 |
47.4 |
0 |
52.6 |
Again, the blended "black" tended to green, and since a suitable alternative blue
pigment could not be located, it was determined that a major change in the pigment
set was necessary.
Example 3 : Medium containing Green, Violet and Yellow Pigments
[0084] Example 1 was repeated except that the pink and blue pigments were replaced with
Clariant Hostaperm Violet RL02 and Clariant Novoperm Yellow 4G VP2532 from the same
manufacturer. The former is a dioxazine pigment stated by the manufacturer to have
a specific gravity of 1.49, a surface area of 80 m
2/g, and an average particle size of 50 nm, while the latter is a disazo pigment stated
by the manufacturer to have a specific gravity of 1.44, a surface area of 33 m
2/g, and an average particle size of 162 nm. Again, the millbases were also blended
to produce a mixed dispersion having a color as close to black as possible. The results
are shown in Table 3 below.
Table 3
| Color (saturated) |
L* |
a* |
b* |
%G |
%P |
%Y |
| Green |
21.1 |
10.1 |
-28.5 |
100 |
0 |
0 |
| Purple |
30.4 |
4.2 |
20.8 |
0 |
100 |
0 |
| Yellow |
46.2 |
-2.7 |
85.2 |
0 |
0 |
100 |
| Black |
31.0 |
0 |
0 |
57.8 |
22.9 |
19.3 |
As may be seen from Table 3, the blend of this set of pigments produces a good, neutral
black.
[0085] A polymer-dispersed electrophoretic medium was produced using this black blend in
substantially the same manner as described in Example 1 of
U. S. Patent No. 6,866,760; the polymer-dispersed medium was coated on the indium-tin-oxide (ITO) coated surface
of a polyethylene terephthalate/ITO film, dried, and adhesive layer applied, and the
resultant film laminated to a rear electrode to produce an experimental single-pixel
display, which were then driven at various combinations of drive voltages and frequencies.
[0086] In such a multi-pigment display, if all the pigments are packed, the display appears
open (substantially transparent); if all the pigments are dispersed the display appears
closed (substantially black). When the fractions of each pigment
in its dispersed form is different from the overall proportion of that pigment in the display (i.e., different
from the 57.8% green, 22.9% violet, 19.3% yellow shown in Table 3), then the display
color approaches the color of the more dispersed pigment. For example, if the yellow
pigment is well dispersed, and the green and purple pigments are packed, the display
will appear yellow. Alternatively, if the yellow and green pigments are dispersed
and only the purple is packed, the display will appear yellow-green. Table 4 below
gives examples of applied waveforms and the corresponding colors produced.
Table 4
| Color |
L* |
a* |
b* |
Waveform |
| OPEN |
53.0 |
-4.2 |
4.9 |
120V, 5kHz sine wave |
| CLOSED |
24.7 |
-3.3 |
-2.5 |
120V, 60Hz sine wave |
| GREEN |
42.2 |
-25.9 |
8.2 |
120V, 0.5Hz square wave |
| YELLOW |
47.0 |
-5.8 |
16.7 |
Open, then 10ms bursts of 2kHz sine wave, 0.5seconds apart |
| BLUE |
26.6 |
0.2 |
-13.3 |
120V, 1.2kHz sine wave |
The above colors, and others produced using different waveforms, are plotted in the
a*b* plane in Figure 17 of the accompanying drawings. The colors were measured with
an Eye-One spectrophotometer in reflective mode with a white background placed behind
the sample. The white background was treated as the reference white-point for the
L*a*b* calculations.
[0087] It will be seem from the Figure that the experimental display was capable of displaying
a substantial color gamut, though only in the green/yellow/blue portion of the a*b*
plane; this particular display was not capable of producing a positive a* (i.e., a
red color). However, in view of the substantial color gamut capable of being displayed
by this experimental display, and the wide range of pigments commercially available
and suitable for incorporation in such a display it can be anticipated that evaluation
of additional pigments and further work in formulation will produce displays have
a broader color gamut more centered in the a*b* plane.
Example 4 : Coating slurry for cyan shuttering capsules
[0088] A cyan pigment, Irgalite Blue GLVO (available from BASF, Ludwigshafen, Germany) (8
g) was combined with Isopar E (12 g) and a solution of Solsperse 17000 (available
from Lubrizol Corporation, Wickliffe, OH, 20 g of a 20% w/w solution in Isopar E)
and the mixture was dispersed by stirring with beads to afford a cyan pigment dispersion.
[0089] The cyan pigment dispersion thus prepared (5.75 g) was combined with Isopar E (109.25
g) and the resultant mixture mechanically rolled overnight to produce an internal
phase ready for encapsulation. The internal phase so prepared was then encapsulated
following the procedure described in
U.S. Patent No. 7,002,728. The resultant encapsulated material was isolated by sedimentation, washed with deionized
water, and size separated by sieving, using sieves of 45 and 20 µm mesh. Analysis
using a Coulter Multisizer showed that the resulting capsules had a mean size of 40
µm and more than 85 percent of the total capsule volume was in capsules having the
desired size of between 20 and 60 µm.
[0090] The resulting capsule slurry was adjusted to pH 9 and excess water removed. The capsules
were then concentrated and the supernatant liquid discarded. The capsules were mixed
with an aqueous polyurethane binder (prepared in a manner similar to that described
in
U. S. Patent Application No. 2005/0124751) and small amounts of Triton X-100 surfactant and hydroxypropylmethyl cellulose were
added and mixed thoroughly to provide a slurry ready for use in a display, as described
in detail below.
Example 5 - Coating slurry for cyan shuttering capsules containing 1% w/w of pigment
[0091] Irgalite Blue GLVO (26 g) was combined with Isopar E (70 g) and a solution of Solsperse
17000 (70 g of a 20% w/w solution in Isopar E) and the mixture was dispersed in an
attritor with glass beads to produce a cyan pigment dispersion. The cyan pigment dispersion
thus prepared (5.75 g) was combined with Isopar E (109.25 g). The resultant mixture
was mechanically rolled overnight to produce an internal phase ready for encapsulation.
The internal phase so prepared was then encapsulated following the procedure of Example
4 above to produce capsules having a mean size of 40 µm and with more than 85 percent
of the total capsule volume in capsules having the desired size of between 20 and
60 µm. The capsules were then incorporated into a coating slurry in the same way as
in Example 4 above.
Example 6 - Coating slurry for magenta shuttering capsules
[0092] A magenta pigment, Quindo Red 19 (available from Sun Chemical Corporation, Parsippany,
NY) was provided with a poly(lauryl methacrylate) coating substantially as described
in
U.S. Patent No. 7,002,728. The coated pigment (13 g) was then combined with Isopar E (30 g) to produce a magenta
pigment dispersion, which was filtered through a 200 µm mesh film and the per cent
solids determined to be 17%.
[0093] The magenta pigment dispersion thus prepared (13 g) was combined with Isopar E (88
g) and Solsperse 17000 (8 g of a 20% w/w solution in Isopar E), and the resultant
mixture was rolled mechanically overnight to produce an internal phase ready for encapsulation.
The internal phase so prepared was then encapsulated as described in Example 4 above
to produce capsules having a mean size of 40 µm and with more than 85 percent of the
total capsule volume in capsules having the desired size of between 20 and 60 µm.
The capsules were then incorporated into a coating slurry in the same way as in Example
4 above.
Example 7 - Coating slurry for magenta/white vertically switching capsules
[0094] Functionalized magenta pigment (10 g, prepared as described in Example 6 above) was
combined with Isopar E (40 g) and the resultant mixture dispersed by stirring with
beads to produce a magenta pigment dispersion, which was filtered through a 200 µm
mesh film and the percent solid determined. This dispersion (18.82 g) was combined
with titanium dioxide (R794 available from E. I. du Pont de Nemours Corporation, Wilmington,
DE) (70.57 g of a 60% w/w dispersion treated as described in
U.S. Patent No. 7,002,728), minor amounts of Solsperse 17000 and poly(isobutylene) of molecular weight 600,000,
and additional amounts of Isopar E. The resultant mixture was rolled mechanically
overnight to produce an internal phase ready for encapsulation. The internal phase
so prepared was then encapsulated as described in Example 4 above to produce capsules
having a mean size of 40 µm and with more than 85 percent of the total capsule volume
in capsules having the desired size of between 20 and 60 µm. The capsules were then
incorporated into a coating slurry in the same way as in Example 4 above.
Example 8 - Coating slurry for yellow/white vertically switching capsules.
[0095] A yellow pigment, Paliotan Yellow L 1145 (available from BASF), was surface-treated
with N-[3-(trimethoxysilyl)propyl]-N'-(4-vinylbenzyl)ethylenediamine hydrochloride,
followed by provision of a poly(lauryl methacrylate) coating substantially as described
in
U.S. Patent No. 7,002,728. This yellow pigment (30 g) was combined with Isopar E (70 g) and sonicated for 2
hours and mechanically rolled overnight. The resultant dispersion (45.6 g) was then
combined with the same R794 titanium dioxide as in Example 7 (102.6 g of a 60% w/w
dispersion) minor amounts of Solsperse 17000 and poly(isobutylene) of molecular weight
850,000, and additional amounts of Isopar E. The resultant mixture was rolled mechanically
overnight to produce an internal phase ready for encapsulation. The internal phase
so prepared was then encapsulated as described in Example 4 above to produce capsules
having a mean size of 40 µm and with more than 85 percent of the total capsule volume
in capsules having the desired size of between 20 and 60 µm. The capsules were then
incorporated into a coating slurry in the same way as in Example 4 above.
Example 9 - Coating slurry for capsules containing no pigment.
[0096] A solution of Solsperse 17000 in Isopar E) was rolled mechanically overnight to produce
an internal phase ready for encapsulation. The internal phase so prepared was then
encapsulated as described in Example 4 above to produce capsules having a mean size
of 40 µm and with more than 85 percent of the total capsule volume in capsules having
the desired size of between 20 and 60 µm. The capsules were then incorporated into
a coating slurry in the same way as in Example 4 above.
Example 10 - Assembly and switching of a cyan/yellow bichrome display
[0097] The cyan shuttering capsule slurry prepared in Example 4 above was coated on to a
125 µm poly(ethylene terephthalate) (PET) film bearing a printed hexagonal grid metallic
electrode of 50 µm pitch and 1 µm line width using a bar coater with a 50 µm gap.
The coating was dried at 60°C, following which a second coating of capsules was applied
using the yellow/white vertical switching capsule slurry prepared as described in
Example 8 above, with a bar coater gap of 100 µm. The second coating layer was dried
at 60°C. A layer of polyurethane adhesive doped with a tetraalkylammonium salt, pre-coated
onto a release sheet, was laminated on top of the second layer of capsules as described
in
U.S. Patent No. 7,002,728. The release sheet was removed and the resultant multilayer structure was laminated
onto a graphite rear electrode. As finally assembled the display structure comprised,
in order from its viewing surface, a first layer of PET film base, a second layer
of patterned electrode, a third layer of cyan shuttering capsules, a fourth layer
of yellow/white vertically switching capsules, a fifth layer of a conductively doped
lamination adhesive, and a sixth layer comprising a graphite rear electrode.
[0098] The display structure so produced was driven by applying a square wave AC signal
at 30 Hz and +/- 10 V that was offset by DC voltages that ranged from 40 V to -40
V. As the display was driven it was illuminated by a tungsten ring-light source and
light reflected from the display was analyzed spectrophotometrically, giving the L*a*b*
values shown in Table 5 below.
Table 5
| Time (s) |
Offset Voltage |
L* |
a* |
b* |
| 1 |
40 |
47.83 |
-22.68 |
-22.03 |
| 2 |
30 |
49.11 |
-21.02 |
-20.92 |
| 3 |
20 |
49.24 |
-21.07 |
-21.20 |
| 4 |
10 |
48.53 |
-22.38 |
-22.52 |
| 5 |
0 |
41.32 |
-37.16 |
-33.34 |
| 6 |
-10 |
41.67 |
-35.22 |
-7.91 |
| 7 |
-20 |
44.86 |
-29.27 |
6.13 |
| 8 |
-30 |
46.81 |
-27.42 |
8.74 |
| 9 |
-40 |
47.86 |
-25.45 |
9.46 |
| 10 |
-30 |
48.27 |
-24.84 |
10.14 |
| 11 |
-20 |
48.29 |
-24.97 |
10.16 |
| 12 |
-10 |
47.42 |
-26.88 |
9.60 |
| 13 |
0 |
41.09 |
-42.04 |
2.31 |
| 14 |
10 |
41.84 |
-36.48 |
-15.86 |
| 15 |
20 |
46.37 |
-25.72 |
-21.39 |
| 16 |
30 |
48.33 |
-22.44 |
-21.64 |
| 17 |
40 |
49.11 |
-21.16 |
-20.17 |
| 18 |
30 |
49.31 |
-20.89 |
-19.84 |
| 19 |
20 |
49.26 |
-21.10 |
-20.09 |
| 20 |
10 |
48.60 |
-22.24 |
-21.40 |
| 21 |
0 |
41.77 |
-36.03 |
-31.51 |
[0099] These results are shown graphically in Figures 13A and 13B. Figure 13A shows the
L*, a* and b* values as a function of the DC offset applied to the 30Hz AC drive at
the top-plane, transparent electrode. Note that similar states are obtained with a
simple DC drive, without the 30Hz AC component, although the resultant states are
slightly inferior.
[0100] This display operates as shown in Figures 8A-8D. The first layer of capsules, in
contact with the concentrator electrodes on the top-plane side and with the second
layer of capsules on the other, contains a positively-charged cyan pigment. When the
DC offset is positive, the cyan pigment is shuttered at the junction between the first
layer of capsules and the second layer of capsules (as shown in Figure 8C). When the
DC offset is negative, the cyan pigment collects at the concentrator electrodes (as
shown in Figure 8A). As the DC offset moves towards zero the pigment moves away from
the shuttered state. The hysteresis loop seen in the a* value in Fig 13A reflects
these changes (less negative a* corresponds to the shuttered cyan pigment). There
is a slight hysteresis, as the movement of pigment towards the shuttered state as
the DC offset is increased is faster than the movement away from the shuttered state
as the DC offset is decreased.
[0101] The vertically-switching capsules (i.e., capsules in which the particles move parallel
to the applied electric field) in the second capsule layer contain a positively-charged
yellow pigment and a negatively-charged white pigment, and thus when the top-plane
is negatively charged this layer of capsules displays a yellow image (positive b*)
and when the top-plane is positively charged a white image (negative b* because of
the blue component in the overlying cyan layer).
[0102] The a*/b* plot shown in Figure 13B corresponds experimentally to that shown conceptually
in Figure 9B.
Example 11 - Assembly and driving of a cyan/magenta bichrome display in which a layer
of pigment-less capsules is used to direct shuttering.
[0103] The display produced in this Example has the structure shown in Figure 12A.
[0104] The pigment-less capsule slurry prepared in Example 9 above was coated on to a PET
film having a transparent, conductive coating of indium tin oxide (ITO) and dried
using the same conditions as the first layer of capsules in Example 10 above. A second
coating of capsules was applied using the cyan shuttering capsule slurry prepared
in Example 5, above, with a bar coater gap of 80 µm, and the coating was dried at
60°C. A third coating of capsules was applied using the magenta/white vertical switching
capsule slurry prepared in Example 7 above using a bar coater gap of 100 µm to form
a third capsule layer, which was dried at 60°C. An adhesive layer was laminated on
top of the third layer of capsules in the same manner as in Example 10 above. The
release sheet was removed and the resultant multilayer structure was laminated onto
a graphite rear electrode. As finally assembled the display structure comprised, in
order from its viewing surface, a first layer of PET film base, a second layer of
an unpatterned, continuous transparent electrode, a third layer of pigment-less capsules,
a fourth layer of cyan shuttering capsules, a fifth layer of magenta/white vertically
switching capsules, a sixth layer of adhesive, and a seventh layer comprising the
graphite rear electrode.
[0105] The display structure so produced was driven by applying a square wave AC signal
at 30 Hz and +/- 10 V that was offset by DC voltages that ranged from 40 V to -40
V. As the display was driven it was illuminated by a tungsten ring-light source and
light reflected from the display was analyzed spectrophotometrically, giving the L*a*b*
values shown in Table 6 below.
Table 6
| Time (s) |
Offset Voltage |
L* |
a* |
b* |
| 1 |
40 |
47.55 |
-29.33 |
-41.46 |
| 2 |
30 |
49.64 |
-25.95 |
-38.86 |
| 3 |
20 |
49.35 |
-25.66 |
-38.95 |
| 4 |
10 |
48.27 |
-26.97 |
-40.10 |
| 5 |
0 |
44.22 |
-34.81 |
-46.48 |
| 6 |
-10 |
39.55 |
-30.70 |
-45.24 |
| 7 |
-20 |
31.31 |
-5.77 |
-37.80 |
| 8 |
-30 |
31.21 |
4.53 |
-33.22 |
| 9 |
-40 |
32.80 |
5.97 |
-31.11 |
| 10 |
-30 |
32.88 |
5.63 |
-30.99 |
| 11 |
-20 |
32.32 |
4.83 |
-31.93 |
| 12 |
-10 |
31.22 |
3.01 |
-33.67 |
| 13 |
0 |
28.32 |
-2.14 |
-37.97 |
| 14 |
10 |
29.82 |
-6.63 |
-38.78 |
| 15 |
20 |
41.69 |
-20.62 |
-40.66 |
| 16 |
30 |
48.19 |
-23.62 |
-39.06 |
| 17 |
40 |
50.44 |
-23.52 |
-37.55 |
| 18 |
30 |
50.43 |
-23.76 |
-37.58 |
| 19 |
20 |
49.76 |
-24.34 |
-38.09 |
| 20 |
10 |
48.60 |
-25.70 |
-39.86 |
| 21 |
0 |
44.52 |
-33.51 |
-45.99 |
[0106] These results are shown graphically in Figures 14A and 14B. Figure 14A shows the
L*, a* and b* values as a function of the DC offset applied to the 30Hz AC drive at
the top-plane, transparent electrode. Note that, as was the case in Example 10 above,
similar states are obtained with a simple DC drive, without the 30Hz AC component,
although the resultant states are slightly inferior.
[0107] The display operates as follows. The second layer of capsules, in contact with the
pigment-less capsules on one side and with the third layer of capsules on the other,
contains a positively-charged cyan pigment and shutters as shown conceptually in Figure
4. When the DC offset is positive, the cyan pigment is shuttered at the junction between
the second layer of capsules and the third layer of capsules. When the DC offset is
negative, the cyan pigment is shuttered at the junction between the second layer of
capsules and the first layer of (pigment-less) capsules. The shuttering of the cyan
pigment is most easily seen in the a*/b* plot shown in Figure 14B, in which arrow
i corresponds to the movement between shuttered and unshuttered cyan pigment when
the top-plane is positively charged and arrow ii corresponds to the movement between
shuttered and unshuttered cyan pigment when the top plane is negatively charged.
[0108] The vertically-switching capsules contain a positively-charged magenta pigment and
a negatively-charged white pigment, and thus when the top plane is negatively charged
this layer of capsules displays a magenta image (more positive a*) and when positive
a white image (more negative a*). This switching corresponds to arrow iii in Figure
14B.
Example 12 - Cyan/magenta/yellow trichrome display as per Figure 12A.
[0109] The first two coating steps of Example 10 above were repeated using the magenta shuttering
capsule slurry prepared in Example 6 above for the first coated layer and the cyan
shuttering capsule slurry prepared in Example 5 above for the second coated layer,
except that in the second coating the bar coater gap was 80 µm. Next, the yellow/white
vertical switching capsule slurry prepared in Example 8 above was applied with a bar
coater gap of 100 µm to form a third capsule layer, which was dried at 60°C. An adhesive
layer was laminated on top of the third layer of capsules, the release sheet removed
and the remaining layers laminated on to a graphite rear electrode, all as in Example
10. As finally assembled the display structure comprised, in order from the viewing
surface, a first layer of PET film base, a second layer of patterned electrode, a
third layer of magenta shuttering capsules, a fourth layer of cyan shuttering capsules,
a fifth layer of yellow/white vertically switching capsules, a sixth layer of a conductively
doped lamination adhesive, and a seventh layer comprising a graphite rear electrode.
[0110] The display structure was driven, illuminated and the light reflected therefrom analyzed,
all in the same manner as in Example 10. The results are shown in Table 7 below.
Table 7
| Time (s) |
Offset Voltage |
L* |
a* |
b* |
| 1 |
40 |
47.48 |
16.47 |
-4.23 |
| 2 |
20 |
48.75 |
15.92 |
-3.60 |
| 3 |
10 |
48.15 |
16.30 |
-3.88 |
| 4 |
5 |
46.92 |
16.95 |
-4.92 |
| 5 |
0 |
42.25 |
17.44 |
-9.20 |
| 6 |
-5 |
39.03 |
12.09 |
-8.61 |
| 7 |
-10 |
39.68 |
11.03 |
8.37 |
| 8 |
-20 |
42.35 |
9.32 |
19.65 |
| 9 |
-40 |
46.18 |
6.57 |
24.16 |
| 10 |
-20 |
46.33 |
6.44 |
24.11 |
| 11 |
-10 |
45.27 |
7.52 |
23.62 |
| 12 |
-5 |
43.35 |
9.36 |
21.91 |
| 13 |
0 |
39.31 |
10.41 |
18.79 |
| 14 |
5 |
37.75 |
8.03 |
16.43 |
| 15 |
10 |
42.03 |
11.98 |
13.69 |
| 16 |
20 |
46.61 |
14.71 |
5.12 |
| 17 |
40 |
49.76 |
13.57 |
-0.67 |
| 18 |
20 |
50.09 |
13.55 |
-1.86 |
| 19 |
10 |
49.37 |
14.05 |
-2.72 |
| 20 |
5 |
47.99 |
14.97 |
-3.76 |
| 21 |
0 |
43.20 |
16.23 |
-7.40 |
These results are shown graphically in Figures 15A and 15B which are directly comparable
to the Figures 13A and 13B respectively. It can be seen that a wide range of colors
is addressable by the display. The colors are offset along the a* axis, indicating
that the magenta shutter is not fully closing. Such an offset may be corrected by
applying a uniform color filter to the entire display.
Example 13 - Bichrome display using a single applied voltage and time modulation.
[0111] A display was prepared essentially as described in Example 11 above, except that
the ITO coating on the PET was pretreated with a composition comprising an ionic dopant
prior to application of the pigment-less capsule layer. This display was addressed
by using the waveform shown in Table 8 below.
Table 8
| Start time |
End time |
Voltage (V) |
Fig. 16A ref. |
| 0 |
2 |
-30 |
a |
| 2 |
4 |
0 |
b |
| 4 |
6 |
30 |
c |
| 6 |
8 |
0 |
d |
| 8 |
8.2 |
-30 |
e |
| 8.2 |
10.2 |
0 |
f |
The drive continued with pulses at 30V of 200 ms length followed by rests of 2 seconds
in length. The colors produced by the display are shown in Figure 16, in which the
letters correspond to those in the last column of Table 8. A negative voltage shutters
the cyan pigment and switches the magenta/white capsules to magenta, corresponding
to position a in Figure 16. As the voltage is held at zero, the magenta/white capsules,
being state-stable, remain in the magenta state but the cyan shutter, not being state-stable,
relaxes to the cyan state from the clear state, corresponding to position b in Figure
16. A positive voltage then switches the cyan to the shuttered, clear state and the
magenta to the white state, corresponding to position c in Figure 16. As the voltage
is held at zero, the magenta/white capsules, being state-stable, remain in the white
state but the cyan shutter, not being state-stable, relaxes to the cyan state from
the clear state, corresponding to position d in Figure 16. Next the polarity of the
drive is reversed, but the switching time is reduced to 200 ms in pulses separated
by 2 second rests. The magenta/white capsules are incrementally switched from the
white to the magenta state (since they are state-stable), whereas the cyan capsules
partially shutter (position e) but relax to the non-shuttered state every time the
voltage is reduced to zero (position f). This pattern repeats as the short pulses
are continued.
[0112] From the foregoing discussion, it will be seen that the present invention provides
variable transmission electrophoretic media capable of displaying multiple colors.
When used as a variable color segmented overlay, the media of the present invention
can provide a much broader color gamut than a conventional (static) color filter array.
The present invention also provides a low haze monochrome variable transmission medium
with high image stability.